CN112239537B - Long-acting high-temperature-resistant block polyamide composition and fiber and preparation method thereof - Google Patents
Long-acting high-temperature-resistant block polyamide composition and fiber and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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Abstract
The invention discloses a long-acting high-temperature-resistant block polyamide composition and a fiber and a preparation method thereof, wherein the long-acting high-temperature-resistant block polyamide composition comprises the following components: a copolymer having the following unit structure I and unit structure II, a copper-based high temperature resistant agent, and (3) a stabilizer, the chain end of which contains 3 kinds of end structural groups: the invention adopts special monoacid to carry out structural modification on the tail end of a polymer molecular chain, controls the content of various groups at the tail end of the chain, and the prepared block polyamide copolymer composition still maintains more than 70 percent of tensile strength after being placed at 180 ℃ for 800 hours, and has good spinnability effect.
Description
Technical Field
The invention relates to a block polyamide, a preparation method thereof and a fiber.
Background
The polyamide can be obtained by polycondensation of diamine and diacid or ring opening of cyclic amide of different types, and the variety of raw material types endows the polyamide with changeable properties, such as excellent toughness, wear resistance, self-lubricity and the like, and the polyamide can be used as engineering plastics for extrusion or injection molding, can also be spun into fiber products, and the application field of the polyamide is widened continuously. With the continuous development of the automobile industry, the application of polyamide to automobiles has been greatly developed, and the development of automobiles has also placed higher demands on the safety of materials, for example, polyamide fibers used as tire frame materials are required to have excellent high temperature resistance and weather resistance. At present, in the preparation of polyamide for spinning and in the spinning process, the problem of difficulty in both heat resistance and spinnability exists, so that the related research on high-temperature resistant polyamide for spinning is increasing.
Patent CN201210068271.1 reports a high temperature resistant polyamide fiber, after the semi-aromatic polyamide and polyolefin are melt blended and spun to obtain a blended fiber, the polyolefin in the fiber is removed by adopting a solvent to finally obtain an ultrafine heat resistant fiber, but the adopted organic solvent has certain toxicity, has hidden environmental pollution and is difficult to realize large-scale production.
The patent CN201711458097.0 adopts the copolymerization of the pentanediamine, the hexanediamine and the adipic acid to prepare the high-weather-resistant polyamide 66 with high molecular weight (26000-28000) and moderate viscosity (66-74) and the fiber thereof. However, the applicant cannot prepare the samples and performances according to the patent, and the samples and performances are not feasible, and in addition, no data in the patent indicate that the materials have long-time high-temperature resistance. Patent CN00110195.1 discloses a polyamide 66 high temperature resistant and antioxidant fiber, which is prepared by adding copper acetate, potassium iodide and rare earth stearate mixed antioxidant into polyamide 66 and blending the mixture with silk, and the original fiber characteristic can be maintained at high temperature, however, the product additive prepared by the method has uneven dispersion and poor spinnability.
Unfortunately, the spinnability of the polyamide is not improved but the long-term high temperature resistance is difficult to realize, and the application range of the polyamide is limited because the high temperature resistant polyamide material which is not prepared is difficult to spin.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and discloses a long-acting high-temperature-resistant block polyamide copolymer composition and fiber and a preparation method thereof.
The long-acting high-temperature-resistant block polyamide copolymer composition comprises the following components:
(1) A copolymer having the following unit structure I and unit structure II,
Unit structure I:
unit structure II:
(2) Copper-based high-temperature resistant agent
(3) Stabilizing agent
The content of the copper high-temperature resistant agent is 0.1-0.8% of the total mass of the composition;
the content of the auxiliary agent is 0.05-0.2% of the total mass of the composition;
the molecular chain end of the long-acting high-temperature-resistant block polyamide copolymer contains 3 end structural groups: primary amino groups, carboxyl groups, groups containing non-primary amino groups and carboxyl groups;
the group containing non-primary amino or carboxyl is obtained by reacting monoacid (A) with amino on a long-acting high-temperature-resistant block polyamide copolymer molecular chain;
the monoacid (A) has the following structure III:
R-COOH
wherein,,
r is 1-12 carbon skeleton structures and derived carbon skeleton structures thereof;
further, R is 1-6 carbon skeleton structures, or 6-12 derived carbon skeleton structures;
further, R is 3 to 6 straight chain or branched chain alkylene groups or 6 to 12 derivative carbon skeleton structures containing a cyclic structure;
further, R is 3-6 branched alkylene groups or 6-12 derivative carbon skeleton structures containing benzene ring structures;
the structure of the monoacid (A) is shown as (a 1) or (a 2):
no other terminal groups other than the 3 terminal groups are contained;
the primary amino group content of the molecular chain terminal is 40-60 mmol/kg;
the carboxyl group content at the tail end of the molecular chain is 55-75 mmol/kg;
the content of the groups containing non-primary amino or carboxyl at the tail end of the molecular chain is 5-15 mmol/kg;
the relative viscosity of the long-acting high-temperature-resistant block polyamide copolymer composition is 2.5-2.8, and the number average molecular weight is 14500-19000;
the copper high-temperature resistant agent consists of the following components in percentage by mass:
5 to 15 percent of copper acetate
30 to 50 percent of potassium iodide
40 to 60 percent of potassium bromide
The stabilizer is a stabilizer with the brand name of Nyiostab s-eed of the Kelain company, and is a hindered amine light stabilizer containing methyl piperidine;
the preparation method of the long-acting high-temperature-resistant block polyamide copolymer composition comprises the following steps:
(1) Mixing the following components in parts by weight, adding water to obtain a solution with the concentration of 50wt%, and keeping the temperature of the solution at 50-65℃:
(2) Heating and maintaining the solution in the step (1) at 130-160 ℃, raising the pressure and maintaining the pressure at 0.2-0.3 MPa, and controlling the total time of the process at 50-70 min;
(3) Continuously heating and keeping the temperature at 210-240 ℃, and raising the pressure and keeping the pressure at 1.6-2.0MPa, wherein the process time is controlled at 20-40 min;
(4) Keeping the pressure unchanged, adding copper high-temperature resistant agent and stabilizing agent, starting stirring at the stirring speed of 60-100 r/min, and continuously heating to 250-260 ℃ for 50-80 min;
(5) Continuously heating to 270-280 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is 0MPa to-0.01 MPa, wherein the process time is controlled to be 40-60 min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
The long-acting high temperature resistant block polyamide copolymer composition particles can be used to prepare fibrous articles, including, for example, polyamide monofilament fibers, polyamide filament fibers, by known techniques such as those reported in patent CN 200810123779.0.
Determination of the amino-terminated content of the long-acting high-temperature-resistant block polyamide copolymer:
titrating the amino content of the sample end by using a full-automatic potentiometric titrator, taking 0.5g of polymer, adding 30ml of 2, 2-trifluoroethanol, heating, observing that the sample is completely dissolved, cooling to room temperature, and titrating the amino content of the end by using a calibrated 0.02mol/L hydrochloric acid standard solution;
determination of the carboxyl end group content of the long-acting high-temperature-resistant block polyamide copolymer:
titrating the carboxyl end group content of a sample by using a full-automatic potentiometric titrator, taking 0.5g of polymer, adding 30ml of 2, 2-trifluoroethanol, heating, observing that the sample is completely dissolved, cooling to room temperature, and titrating the amino end group content by using a calibrated 0.02mol/L sodium hydroxide standard solution;
the terminal of the long-acting high-temperature-resistant block polyamide copolymer contains the group content of non-primary amino or carboxyl: according to the preparation method of the long-acting high-temperature-resistant block polyamide copolymer, after monoacid A is removed from the raw materials, the polyamide with the end groups of amino and carboxyl is prepared. Determining the total amount of end groups of the polymer at the same viscosity and molecular weight; calculating to obtain the content of the groups with the terminal non-primary amino or carboxyl according to the detected terminal amino and terminal carboxyl of the sample;
determination of the relative viscosity of the long-acting high-temperature-resistant block polyamide copolymer:
the relative viscosity of the sample was measured using an Ubbelohde viscometer, 0.25g of polymer was taken and 25ml of 90% H was added 2 SO 4 The solution was heated, and after the sample was observed to be completely dissolved. Cooling to 25 ℃, and respectively measuring the flowing time of the polymer solution and the solvent by using the same viscometer at 25.00+/-0.01 ℃, wherein the ratio of the flowing time of the polymer solution to the flowing time of the solvent is the relative viscosity;
the long-acting high temperature resistant block polyamide copolymer particles obtained by the above method can be used for preparing fiber products including, for example, polyamide monofilament fibers and polyamide filament fibers by known techniques such as those reported in patent CN 200810123779.0.
The beneficial effects of the invention are as follows:
the invention adopts special monoacid to carry out structural modification on the molecular chain end of the polymer, controls the content of various groups at the molecular chain end of the polyamide copolymer, is matched with a specific copper high-temperature resistant agent and a specific stabilizer for use, and the prepared segmented polyamide copolymer has excellent long-acting high-temperature resistant performance, still maintains more than 70 percent of tensile strength after being placed for 800 hours at 180 ℃, and has good spinnability effect.
Detailed Description
The present invention will be described in further detail with reference to examples, but is not limited thereto.
The raw materials involved in the examples are all commercial products and are commercially available;
the copper high-temperature resistant agent related in the embodiment comprises the following components in percentage by mass:
copper acetate 12%
Potassium iodide 34%
Potassium bromide 54%
The monoacids (a) according to the examples have the following structural formulae:
(a1) Is aliphatic monoacid, and has a chemical name of 2, 3-dimethylbutyric acid (CAS No. 14287-61-7);
(a2) Is aromatic monoacid, and has a chemical name of salicylic acid (CAS No. 69-72-7);
the addition amount of the copper high-temperature resistant agent is 0.5% of the total mass of the components;
the addition amount of the Nylostab s-eed stabilizer is 0.1% of the total mass of the components;
examples
The long-acting high-temperature-resistant block polyamide copolymer composition is prepared from the following components in parts by weight:
table 1: the raw materials of each component of examples 1 to 4 were in parts by weight
| Raw materials in parts by weight | Example 1 | Example 2 | Example 3 | Example 4 |
| Hexamethylenediamine | 41.20 | 33.00 | 44.00 | 33.00 |
| Pentanediamine | 1.50 | 3.00 | 1.00 | 3.00 |
| Adipic acid | 53.00 | 45.00 | 55.00 | 45.00 |
| Monobasic acid (a 1) | 0.15 | 0.00 | 0.50 | 0.00 |
| Monobasic acid (a 2) | 0.00 | 0.10 | 0.00 | 0.50 |
Example 1
(1) The components of example 1 in Table 1 were uniformly mixed and desalted water was added to obtain a 50wt% strength solution, and the solution temperature was maintained at 60 ℃ to obtain a solution having a concentration of 50 wt.%:
(2) Heating and maintaining the solution at 145 deg.C, and maintaining the pressure at 0.2MPa for 50min;
(3) Continuously heating and keeping at 230 ℃, and raising and keeping the pressure at 2.0MPa, wherein the process time is controlled at 40min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.5 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.1 percent of the total mass of the components, starting stirring at the stirring speed of 60r/min, and continuously heating to 260 ℃ at the same time, wherein the process time is controlled to be 60min;
(5) Continuously heating to 280 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is at-0.005 MPa, wherein the process time is controlled to be 50min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
The technical content as reported in patent CN200810123779.0 is to prepare a fiber product, which is then spun by methods known in the art to obtain a long-acting high temperature resistant block polyamide copolymer composition fiber.
Example 2
(1) The components of example 2 in Table 1 were uniformly mixed and desalted water was added to obtain a 50wt% strength solution, and the solution temperature was maintained at 50 ℃ C.):
(2) Heating and maintaining the solution at 130deg.C, and maintaining the pressure at 0.3MPa for 50min;
(3) Continuously heating and maintaining at 210 ℃, and raising and maintaining the pressure at 2.0MPa, wherein the process time is controlled at 20min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.8 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.2 percent of the total mass of the components, starting stirring at the stirring speed of 100r/min, and continuously heating to 260 ℃ at the same time, wherein the process time is controlled to be 50min;
(5) Continuously heating to 270 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is at-0.01 MPa, wherein the process time is controlled to be 60min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
And then spinning by a method known in the art to obtain the long-acting high-temperature-resistant block polyamide copolymer composition fiber.
Example 3
(1) The components of example 3 in Table 1 were uniformly mixed and desalted water was added to obtain a 50wt% strength solution, and the solution temperature was maintained at 50 ℃ C.):
(2) Heating and maintaining the solution at 130deg.C, and maintaining the pressure at 0.3MPa for 50min;
(3) Continuously heating and maintaining at 210 ℃, and raising and maintaining the pressure at 2.0MPa, wherein the process time is controlled at 20min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.5 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.05 percent of the total mass of the components, starting stirring at the stirring speed of 100r/min, and continuously heating to 260 ℃ at the same time, wherein the process time is controlled to be 50min;
(5) Continuously heating to 270 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is 0MPa, wherein the process time is controlled to be 50min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
And then spinning by a method known in the art to obtain the long-acting high-temperature-resistant block polyamide copolymer composition fiber.
Example 4
(1) The components of example 4 in Table 1 were mixed uniformly in parts by weight and desalted water was added to obtain a 50wt% strength solution, and the solution temperature was maintained at 65 ℃ C.):
(2) Heating and maintaining the solution at 160deg.C, and maintaining the pressure at 0.3MPa for 70min;
(3) Continuously heating and maintaining at 240 ℃, and raising and maintaining the pressure at 1.6MPa, wherein the process time is controlled at 30min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.3 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.1 percent of the total mass of the components, starting stirring at the stirring speed of 100r/min, and continuously heating to 250 ℃ at the same time, wherein the process time is controlled to be 80min;
(5) Continuously heating to 270 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is 0MPa, wherein the process time is controlled to be 40min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
And then spinning by a method known in the art to obtain the long-acting high-temperature-resistant block polyamide copolymer composition fiber.
Comparative example
Comparative examples 1 to 4 were obtained using the components in parts by weight as shown in Table 2:
table 2: comparative examples 1 to 4 parts by weight of the raw materials of the respective components
| Raw materials in parts by weight | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Hexamethylenediamine | 41.20 | 44.80 | 41.20 | 33.00 |
| Pentanediamine | 1.30 | 1.00 | 0.00 | 0.00 |
| Adipic acid | 53.00 | 55.00 | 53.00 | 45.00 |
| Caprolactam | 0.00 | 0.00 | 0.00 | 3.00 |
| Monobasic acid (a 1) | 0.00 | 0.00 | 0.15 | 0.00 |
| Monobasic acid (a 2) | 0.00 | 0.00 | 0.00 | 0.50 |
| Terephthalic acid | 0.15 | 0.00 | 0.00 | 0.00 |
Comparative example 1
(1) The components of comparative example 1 in Table 2 were uniformly mixed and desalted water was added to obtain a 50wt% strength solution, and the temperature of the solution was maintained at 50℃:
(2) Heating and maintaining the solution at 130deg.C, and maintaining the pressure at 0.3MPa for 50min;
(3) Continuously heating and maintaining at 210 ℃, and raising and maintaining the pressure at 2.0MPa, wherein the process time is controlled at 20min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.3 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.1 percent of the total mass of the components, starting stirring at the stirring speed of 100r/min, and continuously heating to 260 ℃ at the same time, wherein the process time is controlled to be 50min;
(5) Continuously heating to 270 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is 0MPa, wherein the process time is controlled to be 60min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
And then spinning by a method known in the art to obtain the long-acting high-temperature-resistant block polyamide copolymer composition fiber.
Comparative example 2
(1) The components of comparative example 2 in Table 2 were uniformly mixed and desalted water was added to obtain a 50wt% strength solution, and the temperature of the solution was maintained at 50℃:
(2) Heating and maintaining the solution at 130deg.C, and maintaining the pressure at 0.3MPa for 50min;
(3) Continuously heating and maintaining at 210 ℃, and raising and maintaining the pressure at 2.0MPa, wherein the process time is controlled at 20min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.2 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.05 percent of the total mass of the components, starting stirring at the stirring speed of 100r/min, and continuously heating to 260 ℃ at the same time, wherein the process time is controlled to be 50min;
(5) Continuously heating to 270 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is 0MPa, wherein the process time is controlled to be 60min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
And then spinning by a method known in the art to obtain the long-acting high-temperature-resistant block polyamide copolymer composition fiber.
Comparative example 3
(1) The components of comparative example 3 in Table 2 were uniformly mixed and desalted water was added to obtain a 50wt% strength solution, and the temperature of the solution was maintained at 50℃:
(2) Heating and maintaining the solution at 130deg.C, and maintaining the pressure at 0.3MPa for 50min;
(3) Continuously heating and maintaining at 210 ℃, and raising and maintaining the pressure at 2.0MPa, wherein the process time is controlled at 20min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.1 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.05 percent of the total mass of the components, starting stirring at the stirring speed of 100r/min, and continuously heating to 260 ℃ at the same time, wherein the process time is controlled to be 50min;
(5) Continuously heating to 270 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is 0MPa, wherein the process time is controlled to be 60min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
And then spinning by a method known in the art to obtain the long-acting high-temperature-resistant block polyamide copolymer composition fiber.
Comparative example 4
(1) The components of comparative example 4 in Table 2 were uniformly mixed and desalted water was added to obtain a 50wt% strength solution, and the temperature of the solution was maintained at 50℃:
(2) Heating and maintaining the solution at 130deg.C, and maintaining the pressure at 0.3MPa for 50min;
(3) Continuously heating and maintaining at 210 ℃, and raising and maintaining the pressure at 2.0MPa, wherein the process time is controlled at 20min;
(4) Keeping the pressure unchanged, adding copper high temperature resistant agent accounting for 0.3 percent of the total mass of the components and Nylosiab s-eed stabilizing agent accounting for 0.05 percent of the total mass of the components, starting stirring at the stirring speed of 100r/min, and continuously heating to 260 ℃ at the same time, wherein the process time is controlled to be 50min;
(5) Continuously heating to 270 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is 0MPa, wherein the process time is controlled to be 60min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
And then spinning by a method known in the art to obtain the long-acting high-temperature-resistant block polyamide copolymer composition fiber.
The performance test data for each of the examples and comparative examples are shown in Table 3 below:
TABLE 3 Performance tables for examples 1-4 and comparative examples 1-4
Table 3, performance Table of examples 1 to 4 and comparative examples 1 to 4
*1: the number average molecular weight is determined by Gel Permeation Chromatography (GPC);
*2: the original tensile strength is detected according to the standard ISO 527;
*3: the retention of tensile strength is the ratio of the tensile strength to the original tensile strength of a sample after being placed for 800 hours at 180 ℃;
*4: spinnability the polyamide copolymer obtained was spun using known techniques to see if a uniform size, smooth surface fiber could be obtained.
According to the invention, two different diamine substances are introduced to carry out copolymerization with adipic acid in the polyamide process, in addition, special monoacid is adopted to carry out structural modification on the molecular chain end of a polymer, the content of various groups at the molecular chain end of a polyamide copolymer is controlled, the polyamide copolymer is matched with a specific copper high-temperature resistant agent and a specific stabilizer for use, and the prepared block polyamide copolymer has excellent long-acting high-temperature resistant performance, maintains the tensile strength of more than 70% after being placed for 800 hours at 180 ℃, and has good spinnability effect.
Claims (4)
1. The long-acting high-temperature-resistant block polyamide composition is characterized by comprising the following components:
(1) Copolymers having the following unit structures I and II
Unit structure I:
unit structure II:
(2) Copper-based high-temperature resistant agent
(3) A stabilizer;
the molecular chain end of the long-acting high-temperature-resistant block polyamide copolymer contains 3 end structural groups: primary amino groups, carboxyl groups, groups containing non-primary amino groups and carboxyl groups;
the group containing non-primary amino and carboxyl is obtained by reacting monoacid (A) with amino on a long-acting high-temperature-resistant block polyamide copolymer molecular chain;
the monoacid (A) has the following structure III:
R-COOH
r is branched alkyl with 3-6 carbon atoms or carbon skeleton structure with 6-12 carbon atoms and benzene ring structure;
the primary amino group content of the molecular chain end of the polyamide is 40-60 mmol/kg; the carboxyl group content at the tail end of the molecular chain is 55-75 mmol/kg; the content of the groups containing non-primary amino groups and carboxyl groups at the tail end of the molecular chain is 5-15 mmol/kg;
the relative viscosity of the polyamide is 2.5-2.8, and the number average molecular weight is 14500-19000;
the copper high-temperature resistant agent consists of the following components in percentage by mass:
5 to 15 percent of copper acetate
30 to 50 percent of potassium iodide
40 to 60 percent of potassium bromide
The stabilizer is a hindered amine light stabilizer containing methylpiperidine.
2. The long-acting high-temperature-resistant block polyamide composition according to claim 1, wherein the content of the copper-based high-temperature-resistant agent is 0.1-0.8% of the total mass of the composition;
the content of the stabilizer is 0.05-0.2% of the total mass of the composition.
3. The long-acting high temperature resistant block polyamide composition according to claim 1, wherein said monoacid (a) has a structure as shown in (a 1) or (a 2):
4. the method of preparing a long-acting high temperature resistant block polyamide composition according to claim 1, comprising the steps of:
(1) Mixing the following components in parts by weight, adding water to obtain a solution with the concentration of 50wt%, and keeping the temperature of the solution at 50-65℃:
(2) Heating and maintaining the solution in the step (1) at 130-160 ℃, raising the pressure and maintaining the pressure at 0.2-0.3 MPa, and controlling the total time of the process at 50-70 min;
(3) Continuously heating and keeping the temperature at 210-240 ℃, and raising the pressure and keeping the pressure at 1.6-2.0MPa, wherein the process time is controlled at 20-40 min;
(4) Keeping the pressure unchanged, adding copper high-temperature resistant agent and stabilizing agent, starting stirring at the stirring speed of 60-100 r/min, and continuously heating to 250-260 ℃ for 50-80 min;
(5) Continuously heating to 270-280 ℃, opening a gas discharge valve, releasing pressure to normal pressure, and starting a vacuum pump to ensure that the pressure in the kettle is between-0.005 MPa and-0.01 MPa, wherein the process time is controlled to be 40-60 min;
(6) And (3) keeping the temperature unchanged, and charging high-purity nitrogen of 0.4MPa, and granulating to obtain the long-acting high-temperature-resistant block polyamide copolymer composition particles.
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| JP2016069557A (en) * | 2014-09-30 | 2016-05-09 | 東レ株式会社 | Storage method of polyamide pellet |
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